Magnesium halide-supported titanium (pro)catalysts

Abstract

A magnesium halide-supported titanium procatalyst, a catalyst prepared therefrom, an enhanced catalyst consists essentially of a product of a reaction of the magnesium halide-supported titanium procatalyst and a hydrocarbylaluminoxane. Also methods of preparing the (pro)catalysts, a method of polymerizing an olefin, and a polyolefin made by the polymerization method.

The invention claimed is: 
     
       1. An enhanced catalyst that consists essentially of a product of a reaction of (A) a hydrocarbylaluminoxane and a suspension of (B) a magnesium halide-supported titanium procatalyst in (C) a saturated or aromatic hydrocarbon liquid, wherein the (B) magnesium halide-supported titanium procatalyst has been prepared by contacting (D) a solid particulate consisting essentially of magnesium halide with (E) titanium tetrachloride in the (C) saturated or aromatic hydrocarbon liquid so as to give the (B) magnesium halide-supported titanium procatalyst; wherein the (B) magnesium halide-supported titanium procatalyst further comprises conditioning compound (J1) tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)zirconium. 
     
     
       2. The enhanced catalyst of  claim 1  wherein: (i) the (B) magnesium halide-supported titanium procatalyst is free of Al; (ii) the (B) magnesium halide-supported titanium procatalyst is characterized by a molar ratio of Al/Mg from >0 to <0.05; (iii) the magnesium halide of the (B) magnesium halide-supported titanium procatalyst is magnesium chloride; (iv) the magnesium halide of the (B) magnesium halide-supported titanium procatalyst is magnesium bromide; (v) both (i) and (iii); (vi) both (i) and (iv); (vii) both (ii) and (iii); and (viii) both (ii) and (iv). 
     
     
       3. The enhanced catalyst of  claim 1  wherein: (i) the (D) solid particulate consisting essentially of magnesium halide has a Brunauer, Emmett, Teller (BET) surface area of ≥200 square meters per gram (m 2 /g) as measured by BET Surface Area Method; or (ii) the (D) solid particulate consisting essentially of magnesium halide has been prepared by contacting a solution of (F) a dialkylmagnesium compound dissolved in the (C) saturated or aromatic hydrocarbon liquid with 1.95 to 2.05 mole equivalents of hydrogen halide to give a suspension of the (D) solid particulate consisting essentially of magnesium halide in the (C) saturated or aromatic hydrocarbon liquid; or (iii) both (i) and (ii). 
     
     
       4. The enhanced catalyst of  claim 3  wherein the mole equivalent of the hydrogen halide to the (F) dialkylmagnesium compound is from 2.00 to 2.05. 
     
     
       5. The enhanced catalyst of  claim 1  wherein the (A) hydrocarbylaluminoxane is an alkylaluminoxane, a polymethylaluminoxane, an arylaluminoxane, an aralkylaluminoxane, or a combination of any two or more thereof. 
     
     
       6. The enhanced catalyst of  claim 1  wherein the reaction further comprises contacting the (B) magnesium halide-supported titanium procatalyst with (G) an organoborate or (H) an organoboron. 
     
     
       7. A method of polymerizing an olefin using an enhanced catalyst, the method comprising contacting a polymerizable olefin with the enhanced catalyst of  claim 1  under effective conditions to give a polyolefin product, wherein the effective conditions comprise a slurry process conducted at a temperature from 0° to 100° C., a gas phase process conducted at a temperature from 30° to 120° C., or a solution process conducted at a temperature from 100° to 250° C. 
     
     
       8. The method of  claim 7  wherein the polymerizable olefin comprises a combination of ethylene and at least one (C 3 -C 40 )alpha-olefin and the polyolefin product comprises a poly(ethylene-co-(C 3 -C 40 )alpha-olefin) copolymer. 
     
     
       9. A polyolefin product made by the polymerization method of  claim 7 . 
     
     
       10. A method of polymerizing an olefin using a magnesium halide-supported titanium catalyst, the method comprising contacting a polymerizable olefin with the enhanced catalyst of  claim 1  under effective conditions to give a polyolefin product, wherein the effective conditions comprise a slurry process conducted at a temperature from 0° to 100° C., a gas phase process conducted at a temperature from 30° to 120° C., or a solution process conducted at a temperature from 100° to 250° C. 
     
     
       11. The method of  claim 10  wherein the polymerizable olefin comprises a combination of ethylene and at least one (C 3 -C 40 )alpha-olefin and the polyolefin product comprises a poly(ethylene-co-(C 3 -C 40 )alpha-olefin) copolymer. 
     
     
       12. A method of preparing an enhanced catalyst, the method comprising contacting (A) a hydrocarbylaluminoxane with a suspension of (B) a magnesium halide-supported titanium procatalyst in (C) a saturated or aromatic hydrocarbon liquid, thereby giving the enhanced catalyst, wherein the (B) magnesium halide-supported titanium procatalyst has been prepared by contacting a suspension of (D) solid particulate consisting essentially of magnesium halide in the (C) saturated or aromatic hydrocarbon liquid with (E) titanium tetrachloride so as to give the suspension of the (B) magnesium halide-supported titanium procatalyst in the (C) saturated or aromatic hydrocarbon liquid; wherein the (B) magnesium halide-supported titanium procatalyst further comprises conditioning compound (J1) tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)zirconium. 
     
     
       13. The method of  claim 12  further comprising a preliminary step of preparing the (D) solid particulate consisting essentially of magnesium halide by contacting a solution of (F) a dialkylmagnesium compound dissolved in the (C) saturated or aromatic hydrocarbon liquid with 1.95 to 2.05 mole equivalents of hydrogen halide to give a suspension of the (D) solid particulate consisting essentially of magnesium halide in the (C) saturated or aromatic hydrocarbon liquid. 
     
     
       14. The method of  claim 13  wherein the (F) dialkylmagnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium, butyl-ethyl-magnesium, butyl-octyl-magnesium, or a combination thereof. 
     
     
       15. The method of  claim 13  wherein the mole equivalent of the hydrogen halide to the (F) dialkylmagnesium compound is from 2.00 to 2.05. 
     
     
       16. A magnesium halide-supported titanium procatalyst prepared by contacting (D) a solid particulate consisting essentially of magnesium halide with (E) titanium tetrachloride in (C) a saturated or aromatic hydrocarbon liquid, wherein the (D) solid particulate consisting essentially of magnesium halide has been prepared by contacting a solution of (F) a dialkylmagnesium compound dissolved in (C) saturated or aromatic hydrocarbon liquid with 1.95 to 2.05 mole equivalents of hydrogen halide to give a suspension of the (D) solid particulate consisting essentially of magnesium halide in the (C) saturated or aromatic hydrocarbon liquid; wherein the magnesium halide-supported titanium procatalyst is free of aluminum halides; wherein the magnesium halide-supported titanium procatalyst further comprises conditioning compound (J1) tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)zirconium. 
     
     
       17. A magnesium halide-supported titanium catalyst that is product of contacting the magnesium halide-supported titanium procatalyst of  claim 16  with an activator that is a trialkylaluminum compound. 
     
     
       18. A method of polymerizing an olefin using a magnesium halide-supported titanium catalyst, the method comprising contacting a polymerizable olefin with the magnesium halide-supported titanium catalyst of  claim 17  under effective conditions to give a polyolefin product, wherein the effective conditions comprise a slurry process conducted at a temperature from 0° to 100° C., a gas phase process conducted at a temperature from 30° to 120° C., or a solution process conducted at a temperature from 100° to 250° C.